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TWI359877B - Method of depositing catalyst assisted silicates o - Google Patents

Method of depositing catalyst assisted silicates o Download PDF

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Publication number
TWI359877B
TWI359877B TW096142912A TW96142912A TWI359877B TW I359877 B TWI359877 B TW I359877B TW 096142912 A TW096142912 A TW 096142912A TW 96142912 A TW96142912 A TW 96142912A TW I359877 B TWI359877 B TW I359877B
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Taiwan
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ruthenium
substrate
exposing
precursor
chamber
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TW096142912A
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Chinese (zh)
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TW200831696A (en
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Maitreyee Mahajani
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Applied Materials Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • C23C16/45546—Atomic layer deposition [ALD] characterized by the apparatus specially adapted for a substrate stack in the ALD reactor
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Formation Of Insulating Films (AREA)
  • Chemical Vapour Deposition (AREA)
  • Catalysts (AREA)
  • Semiconductor Memories (AREA)

Description

1359877 爲了避免水和吡啶在達到室之前互相作用，吡啶和水 可使用個別的輸送導管乃至分離注射送氣室，以並流到 室。第 1B圖是根據本發明的一個實施例的注射送氣室 108 a-c的示意性視圖。如在第 1B 圖中所示，每個導管 118a-118d送入到個別的注射送氣室108a-108d。因此，可 防止。比咬-水的相互作用直到°比咬和水達到室。1359877 To prevent water and pyridine from interacting before reaching the chamber, pyridine and water can be separated into the injection plenum using a separate delivery catheter or even into the chamber. Fig. 1B is a schematic view of an injection plenum 108a-c in accordance with one embodiment of the present invention. As shown in Fig. 1B, each of the conduits 118a-118d is fed to an individual injection plenum 108a-108d. Therefore, it can be prevented. The interaction with the bite-water until ° reaches the chamber than the bite and water.

矽前驅物（諸如 HCDS和 TEOS)與铪前驅物（諸如 TDMAH、TEMAH、TDEAH和HfCU)不與吡啶相互作用。 因此，矽前驅物和吡啶可使用相同的導管和注射送氣室並 流到室。在一個實施例中，吡啶和矽前驅物可使用相同的 導管和注射送氣室流到室。在另一實施例中，吡啶和矽前 驅物可使用個別的導管和注射送氣室流到室。另外，給前 驅物和吡啶可使用相同的導管和注射送氣室並流到室。在 一個實施例中，吡啶和铪前驅物可使用相同的導管和注射 送氣室流到室。另一實施例中，吡啶和銓前驅物可使用個 別的導管和注射送氣室流到室。The ruthenium precursors (such as HCDS and TEOS) do not interact with pyridines with ruthenium precursors such as TDMAH, TEMAH, TDEAH, and HfCU. Therefore, the ruthenium precursor and pyridine can be used in the same conduit and injection plenum and flow to the chamber. In one embodiment, the pyridine and ruthenium precursors can be flowed to the chamber using the same conduit and injection plenum. In another embodiment, the pyridine and ruthenium precursors can be flowed to the chamber using separate conduits and injection plenums. Alternatively, the same conduit and injection plenum can be used for the precursor and pyridine and flow to the chamber. In one embodiment, the pyridine and ruthenium precursors can be flowed to the chamber using the same conduit and injection plenum. In another embodiment, the pyridine and ruthenium precursors can be flowed to the chamber using separate conduits and injection plenums.

使用分離注射送氣室和導管並流吡啶和水的可選實施 例爲在將水引入到室之前，將基板暴露於吡啶浸泡。吡啶 浸泡可包含將基板暴露於吡啶，而不用引入其他前驅物或 氧化劑（諸如水）。基板暴露於吡啶的時間可足以用吡啶使 基板飽和。在一個實施例中，吡啶浸泡進行大於約1 0秒的 時間。通過執行吡啶浸泡，足夠的催化劑可存在於室内和 基板表面，以確保當引入水前驅物時存在催化劑。由於吡 啶已經在室中，所以所有的吡啶不會在到達室之前與水相 11 1359877An alternative embodiment of using a separate injection plenum and conduit to pyridine and water is to expose the substrate to pyridine soaking prior to introducing water into the chamber. Pyridine immersion can involve exposing the substrate to pyridine without introducing other precursors or oxidizing agents (such as water). The substrate is exposed to pyridine for a time sufficient to saturate the substrate with pyridine. In one embodiment, the pyridine is soaked for a time greater than about 10 seconds. By performing pyridine soaking, sufficient catalyst can be present in the chamber and on the substrate surface to ensure that the catalyst is present when the water precursor is introduced. Since the pyridine is already in the chamber, all the pyridine will not be in the aqueous phase before reaching the chamber 11 1359877

在給前驅物脈衝之後，可淨化和/或抽吸室 2 0 6 )。可使用的示例性淨化氣體包括惰性氣體（諸：ί 在一個實施例中，淨化氣體可包含氮氣。可柚吸室 淨化氣體和可能存在於室中的任何殘留铪前驅物。 實施例中，不執行抽吸步驟，從而僅執行淨化步驟 地，可去除淨化步驟，從而抽吸室以去除姶前驅物 個實施例中，抽吸可發生在淨化氣體引入之前和之 另一實施例中，淨化和抽吸步驟都可重複。抽吸和/ 可發生多次。在又一實施例中，淨化和抽吸可結合 步驟。 在抽吸和/或淨化之後，可發生吼啶浸泡（步驟 在第一吡啶浸泡之後，可將氧源（諸如水的脈衝）引 (步驟2 1 0 )»當氧源引入到室時，吡啶可以可選地 萆中。如果吡啶與水並流到室中，則吡啶和水將具 入口進入室中，以使水和°比咬不經由相同的導管和 時流入室。 在將氧源脈衝提供到室之後，可如上所述再次； 或淨化室（步驟 2 1 2 )。在抽吸和/或淨化之後，可 行另一吡啶浸泡。之後，可將矽前驅物脈衝到室中 214)。當矽前驅物引入到室中時，吡啶可選地提供麥 在矽前驅物脈衝之後，可再次抽吸和/淨化室（步驟 在抽吸和/或淨化之後，基板可暴露於另一吡 (步驟2 1 8 )。吡啶浸泡可利用與上述吡啶浸泡相同 條件進行。在吡啶浸泡之後，氧化源（諸如 Η20)的 (步驟 口氬）。 以去除 在一個 。可選 ° 在一 後。在 或淨化 爲一個 208 )。 入到室 並流到 有分離 入口同 由吸和/ 選地進 (步驟 丨室中。 2 16)。 啶浸泡 的處理 脈衝可 13 1359877 圖 500 ; 爲了便於理解，盡可能使用相同的附圖標記表示圖中 共有的相同元件。預期在一個實施例中公開的元件可以有 利地用於其他實施例而不用特別敍述。After the precursor is pulsed, the chamber can be purged and/or pumped 2 0 6 ). Exemplary purge gases that may be used include inert gases (a: ί In one embodiment, the purge gas may comprise nitrogen. The pomelo chamber purge gas and any residual ruthenium precursor that may be present in the chamber. In an embodiment, The suction step is performed such that only the purification step is performed, the purification step can be removed, thereby pumping the chamber to remove the ruthenium precursor, and the suction can occur before the introduction of the purge gas and in another embodiment, purification and The aspiration step can be repeated. Suction and / can occur multiple times. In yet another embodiment, the purification and aspiration can be combined with the step. After aspiration and / or purification, acridine soaking can occur (step in the first After pyridine soaking, a source of oxygen (such as a pulse of water) can be introduced (step 2 1 0). » When an oxygen source is introduced into the chamber, the pyridine can optionally be in the crucible. If pyridine and water are cocurrent to the chamber, pyridine And the water will have an inlet into the chamber so that the water and the pressure do not flow through the same conduit and into the chamber. After the oxygen source is pulsed into the chamber, it can be re-used as described above; or the clean room (step 2 1 2 ) in the suction and / or after purification, another pyridine immersion is possible. Thereafter, the ruthenium precursor can be pulsed into the chamber 214). When the ruthenium precursor is introduced into the chamber, the pyridine optionally provides the mai after the ruthenium precursor pulse, again Suction and/or clean room (step after the pumping and / or purification, the substrate can be exposed to another pyridyl (step 2 18). Pyridine soaking can be carried out using the same conditions as the above pyridine soaking. After pyridine soaking, the oxidation source (such as Η20) (step argon). To remove in one. Optional ° after one. In or purify to a 208). Enter into the chamber and flow to the separate inlet with the suction and / select the ground (step In the diverticulum. 2 16) The treatment pulse of the pyridine immersion can be 13 1359877. Figure 500; for ease of understanding, the same reference numerals are used to denote the same elements in the drawings. It is expected that the elements disclosed in one embodiment can be advantageous. It is used in other embodiments without special description.

[主 要 元 件符 號說明】 100 裝 置 102 真 空 室 104 基 板 106 基 座 108 注 射 送氣 室 108ι a- d 導 管 110 氣 室 壁 112 低 壓 側部 114 注 射 板 116 孔 1 1 [8a-d導管 120 流 122 注 射 送氣腔 124 排 氣 增壓 室 126 排 氣 板 128 排 氣 增壓 室 130 氣 室 壁 132 孔 134 導 管 136 排 氣 σ 138 即 流 閥 200 流 程 圖 202 步 驟 204 步 驟 206 步 驟 208 步 驟 2 10 步 驟 212 步 驟 214 步 驟 216 步 驟 2 18 步 驟 220 步 驟 222 步 驟 19 1359877[Main component symbol description] 100 Device 102 Vacuum chamber 104 Substrate 106 Base 108 Injection plenum 108 ι a- d Catheter 110 Gas chamber wall 112 Low pressure side portion 114 Injection plate 116 Hole 1 1 [8a-d conduit 120 flow 122 injection gas supply Cavity 124 Exhaust plenum 126 Exhaust plate 128 Exhaust plenum 130 plenum wall 132 Hole 134 Catheter 136 Exhaust σ 138 Flow valve 200 Flowchart 202 Step 204 Step 206 Step 208 Step 2 10 Step 212 Step 214 Step 216 Step 2 18 Step 220 Step 222 Step 19 1359877

224步驟 226步驟 3 0 0流程圖 302步驟 304步驟 306步驟 308步驟 3 10步驟 312步驟 3 14步驟 3 16步驟 3 1 8步驟 320步驟 322步驟 324步驟 326步驟 4 00流程圖 402步驟 404步驟 406步驟 408步驟 410步驟 412步驟 414步驟 416步驟. 4 1 8步驟 420步驟 422步驟 5 0 0流程圖 502步驟 504步驟 506步驟 508步驟 5 1 0步驟 5 12步驟 5 14步驟 5 16步驟 5 1 8步驟 520步驟 522步驟 20224 Step 226 Step 3 0 0 Flowchart 302 Step 304 Step 306 Step 308 Step 3 10 Step 312 Step 3 14 Step 3 16 Step 3 1 8 Step 320 Step 322 Step 324 Step 326 Step 4 00 Flowchart 402 Step 404 Step 406 Step 408 Step 410 Step 412 Step 414 Step 416 Step. 4 1 8 Step 420 Step 422 Step 5 0 0 Flowchart 502 Step 504 Step 506 Step 508 Step 5 1 0 Step 5 12 Step 5 14 Step 5 16 Step 5 1 8 Step 520 Step 522 Step 20

Claims (1)

1359877 公告本 第卟β 號專利案π年π月修正 A A 法，依序地包含： 十、申請專利範圍： 1. 一種高介電常數矽酸鹽沉積方 (a) 在一室中放置至少一基板； (b) 將該至少一基板暴露於一铪前驅物； (c) 將該至少一基板暴露.於一第一吡啶浸泡； (d) 將該至少一基板暴露於一第一氧化源； (e) 將該至少一基板暴露於一矽前驅物； (f) 將該至少一基板暴露於一第二吡啶浸泡；以及接 著 (g) 將該至少一基板暴露於一第二氧化源。 2. 如申諳專利範圍第1項所述的方法，其中該矽前驅 物選自由六氣二矽烷及肆-乙氧基-矽烷所組成之群組。 3. 如申請專利範圍第1項所述的方法，進一步包含： 將該至少一基板暴露於一淨化氣體。 4. 如申請專利範圍第1項所述的方法，其中該姶前驅 物是選自由肆（二甲基胺）姶（TDMAH)、肆（乙基曱基胺）铪 (TEMAH)、肆（二乙基胺）姶（TDEAH)及四氯化铪（HfCl4)所 組成之群組。 5.如申請專利範圍第1項所述的方法，進一步包含： 21 1359877 J lot. 10 曰修正替換頁 ο 1 重複（b) - (g)步驟一次或多次。 6.如申諳專利範圍第1項所述的方法，其中該第一和 第二氧化源選自由水（H20)、臭氧（03)、氧氣（02)及氧自由 基所組成之群組。 7. 如申請專利範圍第1項所述的方法，其中該矽前驅 物包含六氣二矽烷。 8. 如申請專利範圍第1項所述的方法，其中該矽前驅 物包含肆-乙氧基-矽烷。 9. 如申請專利範圍第1項所述的方法，其中位於該室 中的該至少一基板包括二或更多個基板。 10. 如申請專利範圍第1項所述的方法，其中位於該 室中的該至少一基板包括約50個基板。 11. 如申請專利範圍第1項所述的方法，其中該矽前 驅物為肆-乙氡基-矽烷，且該铪前驅物為肆（二曱基胺）铪 (TDMAH)。 12. —種高介電常數矽酸鹽沉積方法，依序地包含： 221359877 Announcement This 卟β patent case π year π month amendment AA method, in order to contain: X. Patent application scope: 1. A high dielectric constant citrate deposition side (a) Place at least one in a chamber a substrate; (b) exposing the at least one substrate to a precursor; (c) exposing the at least one substrate to a first pyridine soak; (d) exposing the at least one substrate to a first oxidation source; (e) exposing the at least one substrate to a precursor; (f) exposing the at least one substrate to a second pyridine soak; and subsequently (g) exposing the at least one substrate to a second source of oxidation. 2. The method of claim 1, wherein the ruthenium precursor is selected from the group consisting of hexa-dioxane and ruthenium-ethoxy-decane. 3. The method of claim 1, further comprising: exposing the at least one substrate to a purge gas. 4. The method of claim 1, wherein the ruthenium precursor is selected from the group consisting of ruthenium (dimethylamine) ruthenium (TDMAH), ruthenium (ethyl decylamine) ruthenium (TEMAH), ruthenium (II) A group consisting of ethylamine) (TDEAH) and hafnium tetrachloride (HfCl4). 5. The method of claim 1, further comprising: 21 1359877 J lot. 10 曰Revising the replacement page ο 1 Repeating the steps (b) - (g) one or more times. 6. The method of claim 1, wherein the first and second oxidation sources are selected from the group consisting of water (H20), ozone (03), oxygen (02), and oxygen radicals. 7. The method of claim 1, wherein the ruthenium precursor comprises hexa-dioxane. 8. The method of claim 1, wherein the ruthenium precursor comprises ruthenium-ethoxy-decane. 9. The method of claim 1, wherein the at least one substrate located in the chamber comprises two or more substrates. 10. The method of claim 1, wherein the at least one substrate located in the chamber comprises about 50 substrates. 11. The method of claim 1, wherein the ruthenium precursor is ruthenium-ethenyl-decane, and the ruthenium precursor is ruthenium (didecylamine) ruthenium (TDMAH). 12. A high dielectric constant strontium deposition method, comprising: 22 1359877 (a)將至少一基板放置在一室中 (b) 將該至少一基板暴露於一高介電常數前驅物； (c) 將該至少一基板暴露於一第一氧化源和吡啶，該 吡啶和該第一氧化源經過不同的入口流入該室中； (d) 將該至少一基板暴露於一矽前驅物；以及接著 (e) 將該至少一基板暴露於一第二氧化源和吡啶，該 吡啶和該第二氧化源經過不同的入口流入該室中。 13. 如申請專利範圍第12項所述的方法，其中該矽前 驅物選自由六氯二矽烷及肆-乙氧基-矽烷所組成之群組。 14. 如申請專利範圍第13項所述的方法，其中該矽前 驅物包括六氯二矽烷。 15. 如申請專利範圍第13項所述的方法，其中該矽前 驅物包括肆-乙氧基-矽烷。 16. 如申請專利範圍第12項所述的方法，進一步包含： 將該至少一基板暴露於一淨化氣體。 17. 如申請專利範圍第12項所述的方法，其中該高介 電常數前驅物是選自由肆（二曱基胺）铪（TDMAH)、肆（乙基 曱基胺）铪（TEMAH)、肆（二乙基胺）姶（TDEAH)及四氣化姶 23 1359877 所组成之群组的铪前驅物。 正獅1 18.如申請專利範圍第17項所述的方法，其中該氧化 源為 02，該铪前驅物為四氯化铪，且該矽前驅物為肆-乙 氧基-矽烷。 19. 如申請專利範圍第12項所述的方法，進一步包含： 重複（b) - (e)步驟一次或多次。 20. 如申請專利範圍第12項所述的方法，其中該第一 和第二氧化源選自由水（H20)、臭氧（03)、氧氣（02)及氧自 由基所組成之群組。 21.如申請專利範圍第12項所述的方法，其中位於該 室中的該至少一基板包括二或更多個基板。 22. 如申請專利範圍第12項所述的方法，其中位於該 室中的該至少一基板包括約50個基板。 23. —種碎酸給沉積方法，依序地包含： 將至少一基板放置在一室中； 將該至少一基板暴露於一铪前驅物； 將該至少一基板暴露於水和°比咬，該水和°比咬經由不 24 1359877 U ^ If _丨 同的入口流入該室中； 將該至少一基板暴露於六氯二矽烷；以及接著 將該至少一基板暴露於水和吡啶，該水和吡啶經過不 同的入口流入該室中。 24. 如申請專利範圍第23項所述的方法，其中位於該 室中的該至少一基板包括二或更多個基板。 25. 如申請專利範圍第23項所述的方法，其中位於該 室中的該至少一基板包括約50個基板。 26. 如申請專利範圍第23項所述的方法，進一步包含 在將該至少一基板暴露於該铪前驅物之前，將該至少一基 板暴露於吡啶。 251359877 (a) placing at least one substrate in a chamber (b) exposing the at least one substrate to a high dielectric constant precursor; (c) exposing the at least one substrate to a first oxidation source and pyridine, Pyridine and the first source of oxidation flow into the chamber through different inlets; (d) exposing the at least one substrate to a stack of precursors; and then (e) exposing the at least one substrate to a second source of oxidation and pyridine The pyridine and the second source of oxidation flow into the chamber through different inlets. 13. The method of claim 12, wherein the ruthenium precursor is selected from the group consisting of hexachlorodioxane and ruthenium-ethoxy-decane. 14. The method of claim 13, wherein the ruthenium precursor comprises hexachlorodioxane. 15. The method of claim 13, wherein the ruthenium precursor comprises ruthenium-ethoxy-decane. 16. The method of claim 12, further comprising: exposing the at least one substrate to a purge gas. 17. The method of claim 12, wherein the high dielectric constant precursor is selected from the group consisting of ruthenium (didecylamine) ruthenium (TDMAH), ruthenium (ethyl decylamine) ruthenium (TEMAH), A ruthenium precursor of the group consisting of ruthenium (diethylamine) ruthenium (TDEAH) and tetragas hydrazine 23 1359877. The method of claim 17, wherein the oxidation source is 02, the ruthenium precursor is ruthenium tetrachloride, and the ruthenium precursor is ruthenium-ethoxy-decane. 19. The method of claim 12, further comprising: repeating the steps (b) - (e) one or more times. 20. The method of claim 12, wherein the first and second sources of oxidation are selected from the group consisting of water (H20), ozone (03), oxygen (02), and oxygen radicals. The method of claim 12, wherein the at least one substrate located in the chamber comprises two or more substrates. 22. The method of claim 12, wherein the at least one substrate located in the chamber comprises about 50 substrates. 23. A method of depositing a broken acid, comprising: placing at least one substrate in a chamber; exposing the at least one substrate to a precursor; exposing the at least one substrate to water and a bite, The water and the ratio bite flow into the chamber through an inlet that is not 24 1359877 U ^ If _; exposing the at least one substrate to hexachlorodioxane; and then exposing the at least one substrate to water and pyridine, the water And pyridine flows into the chamber through different inlets. 24. The method of claim 23, wherein the at least one substrate located in the chamber comprises two or more substrates. 25. The method of claim 23, wherein the at least one substrate located in the chamber comprises about 50 substrates. 26. The method of claim 23, further comprising exposing the at least one substrate to pyridine prior to exposing the at least one substrate to the tantalum precursor. 25
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US7776395B2 (en) 2010-08-17
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